N-trityl-imidazoles as plant fungicides

ABSTRACT

Plant fungicidal compositions are produced which comprises an amount of a compound of the formula:   WHEREIN R is alkyl of one or two carbon atoms substituted by one to five fluoro moieties, sufficient to be effective for killing, combating or controlling plant fungi, in combination with a solid or liquid diluent or carrier. Methods for killing, combatting or controlling fungal diseases in plants comprise applying to the fungi or to the plant to be protected an effective or toxic amount of the above compound.

United States Patent Buchel et al.

[ 1 May 23, 1972 [54] N-TRITYL-IM'IDAZOLES AS PLANT FUNGICIDES [72]Inventors: Karl-Heinz Buchel, Wuppertal-Elberfeld;

Erik Regel, Wuppertal-Cronenberg; Ferdinand Grewe, Burscheid; HansScheinpflug;

Helmut Kaspers, both of Leverkusen; all of Germany Farbenfabriken BayerAktiengesellsehaft, Leverkusen, Germany [22] Filed: Sept. 2, 1970 [21]Appl.No.: 69,112

[73] Assignee:

Related US. Application Data [62] Division of Ser. No. 789,601, Jan. 7,1969.

[30] Foreign Application Priority Data Jan. 29, 1968 Germany ..P 16 70976.5

[52] US. Cl ....424/273 Primary Examiner.lerome D. GoldbergAttorney.lacobs & Jacobs ABSTRACT Plant fungicidal compositions areproduced which comprises an amount of a compound of the formula:

wherein R is alkyl of one or two carbon atoms substituted by one to fivefluoro moieties, sufficient to be effective for killing, combating orcontrolling plant fungi. in combination with a solid or liquid diluentor carrier. Methods for killing. combatting or controlling fungaldiseases in plants comprise applying to the fungi or to the plant to beprotected an effective or toxic amount of the above compound.

7 Claims, No Drawings N-TRITYL-IMIDAZOLES AS PLANT FUNGICIDES This is adivision of our copending application Serial No. 789,601,filed.lan.7,1969.

The present invention relates to and has for its objects the provisionfor particular new l-[(halo, nitro, cyano, alkyl, alkyoxy, alkylmercaptoand fluoro-alkyl--substituted phenyl)- (bis-phenyl)-methyl]-imidazoles,i.e. certain N-tritylimidazoles, which possess fungicidal properties,active compositions in the form of mixtures of such compounds with solidand liquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating fungi, with other and further objects becoming apparent from astudy of the within specification and accompanying examples.

It is already known that N-trityl-imidazoles of the general formula inwhich X is an alkyl or aryl radical, and R is an aryl radical of theformula in which R" is a halogen atom or a lower alkyl radical, and

n is 0 1 or 2 exhibit fungitoxic properties (compare US. Pat.

However, no N-trityl-imidazoles of the formula (i) stated above areknown in which X is always hydrogen and one of the radicals R issubstituted by R" while the two other radicals R have no substituents.

It has now been found, in accordance with the present invention, thatthe particular new N-trityl-imidazoles of the formula R E IaI CaHs (34min in which R is the same as defined above, and

Hal is a halogen atom, preferably chlorine, is reacted with imidazole(llb) in a polar inert organic solvent at a temperature of from 0 to C,in the presence of an acid binder.

The term solvent as used herein includes mere diluents It is decidedlysurprising that the specific N-trityl-imidazoles according to thepresent invention have a considerably stronger fungitoxic activity thanthe chemically very similar N-' trityl-imidazoles previously known. Theactive compounds according to the present invention therefore representa valuable enrichment of the art.

The course of the reaction can be illustrated by means of the followingreaction mechanism:

Advantageously, in accordance with the present invention, in the variousformulae set forth herein:

R represents o-, mand phalo, such as chloro, bromo, fluoro or iodo,especially chloro, bromo or fluoro, more especially 0-, mand pchloro,o-, mand pfluoro, and p-bromo; or

o-, mand pnitro, especially p-nitro; or

o-, mand pcyano, especially p-cyano; or

o-, mand palkyl having l-3 carbon atoms, such as methyl, ethyl, nandiso-propyl, and the like, especially 0- and p- C, alkyl, andparticularly oand pmethyl;

o-, mand palkoxy having l-3 carbon atoms, such as methoxy, ethoxy, nandiso-propoxy, and the like, especially oand p- C alkoxy, and particularly0- methoxy; or

o-, mand palkylmercapto having l-3 carbon atoms such as methylmercapto,ethylmercapto, nand isopropylmercapto, and the like, especially oand p-C,;, alkylmercapto, and particularly p-methylmercapto; or

o-, mand pfluoro-substituted alkyl having 1-2 carbon atoms such asmethyl, ethyl, and the like, especially fluoro-C,. alkyl having l-Sfluoro substituents, more especially mono-, diand trifluoromethyl, andmono-, di-, tri-, tetraand pentafluoroethyl, and the like, preferablym-fluoro-C alkyl having l-5 fluoro groups, and particularlym-trifluoromethyl.

Preferably, R is o-, mor pchloro, bromo, fluoro, C,-;, alkyl, C alkoxyor fluoro-C alkyl having l-5 fluoro substituents.

ln accordance with particular embodiments of the present invention, R ischloro, bromo, fluoro, methyl, methoxy or trifluoro methyl; or p-chloro,bromo or fluoro; or o-methyl or methoxy.

The trityl-halides required as starting materials are clearlycharacterized by the formula (lla) above.

Some of these starting trityl-halides are known. The new startingtrityl-halides may be prepared in the same manner as the known ones.

Preparation of such starting trityl-halides may be affected as follows:first, the Grignard reagent of the mono-substituted benzene is preparedaccording to the usual methods. The mono-substituted phenylmagnesiumbromide so obtained is then reacted with benzophenone. Theorganometallic complex compound obtained is subjected to hydrolysis, theappropriate alcohol being formed [compare J. Org. Chem., 7, 392 (1942)].

From the alcohols the chlorides can be obtained simply by reaction withanhydrous hydrogen chloride or with thionyl chloride. The hydroxyl groupis replaced by chlorine[compare J. Org. Chem., 7, 392 (1942)].

Of course, the starting imidazole of formula (llb) above is a well knowncompound.

According to the present invention, in the reaction of substitutedtrityl-halides with imidazole, polar inert organic solvents are used assolvents. These include for example, nitriles, such as acetonitrile;sulfoxides, such as dimethylsulfoxide; formamides, such as dimethylformamide; ketones, such as acetone; ethers, such as diethyl ether;nitroalkanes, such as nitromethane; unsymmetrical hydrocarbons, such aschloroform; and the like. Particularly well suited are polar inertorganic solvents which have a dielectric constant of more than 2.4.

The production reaction is carried out in the presence of anacid-binder, i. e. acid-binding agent. Preferably, a suitable excess ofimidazole is used. A tertiary amine may, however, also be added, such astriethylamine or dimethylbenzylamine. But the other organic acid-binderscustomarily employed may also be used.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the work is carried out at substantially between about 100 C,preferably between about 45 90 C.

When carrying out the production process according to the presentinvention, the starting materials are used in a molar ratio of about1:1, with about an equimolar amount of acidbinder. The reaction timesdepend on the reaction temperature and extend from about 3 to 24 hours.When working up, the solvent is removed and the reaction product isfreed from amine hydrochloride by washing with water or, if the aminehydrochloride is sparingly soluble in water, it may be separated with anorganic solvent.

Advantageously, the particular new active compounds according to thepresent invention exhibit a strong fungitoxic activity. Because of theirlow toxicity to warm-blooded animals, they are suitable for the controlof undesired fungus growth. Their good compatibility with higher plantspermits the use of the instant compounds as plant protection agentsagainst fungal plant diseases.

The instant active compounds are particularly suitable for the controlof phytopathogenic fungi on above-the-soil parts of plants, as well asagainst phytopathogenic fungi which attack the plants from the soil.

The instant active compounds exhibit a particularly high fungicidalpotency against powdery mildew fungi from the family of theErysiphaceae, for example against the fungi of the genera Erysiphe,Oidium and Podosphaera; and the like. The active compounds of thepresent invention may, however, also be used with good results for thecontrol of other phytopathogenic fungi, for example fungi which causediseases in rice and ornamental plants. The instant active compoundsshow a good activity against Piricularia oryzae, Pellicularia sasakiiand Cochliobolus miyabeanus, three pathogenic agents which occur inrice, and against Cercospora musae; and the like. Furthermore, thegrowth of Phialasphora cinerescens, a fungus which attacks carnationsfrom the soil, is also inhibited.

The instant active compounds are distinguished by a high effectivenessin very low concentrations and by a good compatibility with plants.Doses higher than necessary for the fungicidal effect can therefore beaccepted by the plants.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withinert conventional pesticidal diluents or extenders, i.e. inertconventional pesticidal dispersible carrier vehicles, such as solutions,emulsions, suspen sions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compounds with conventional pesticidal dispersible liquid diluent carriersand/or dispersible solid carriers optionally with the use of carriervehicle assistants, e.g. conventional pesticidal surface-active agents,including emulsifying agents and/or dispersing agents, whereby, forexample, in the case where water is used as diluent, organic solventsmay be added as auxiliary solvents. The following may be chieflyconsidered for use as carrier vehicles for this purpose: inertdispersible liquid diluent carriers including inert organic solvents,such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etcz),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc), ketones (e.g. acetone, etc), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc); whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e. g. surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polyglycol ethers, magnesium stearate, sodiumoleate, etc.), and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, bactericides, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent, andpreferably 05-90 percent, by weight of the mixture, whereascarriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.00001-2 percent,preferably 0.001-1 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as l) a dispersiblecarrier solid, and/or (2) a dispersible carrier liquid such as an inertorganic solvent and/or water preferably including a surface-activeeffective amount of a carrier vehicle assistant, eg a surface-activeagent, such as an emulsifying agent and/or a dispersing agent, and anamount of the active compound which is effective for the purpose inquestion and which is generally about 0.00001- percent, and preferably0.001-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. in this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing 10-80 percent, preferably 20-60 percent, orgenerally from about 20 to about 95 percent by weight of the activecompound, or even the percent active substance alone, e.g. about lO-lOOpercent by weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprises applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally effective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring, and thelike.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration ranges.

The fungicidal effectiveness of the new compounds of the presentinvention is illustrated, without limitation, by the following examples.

EXAMPLE 1 Podosphaera Test (powdery mildew of apples) [Protective]Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weightalkylaryl polyglycol ether Water: 95.0 parts by weight The amount of theparticular active compound required for the desired concentration ofsuch active compound in the spray liquid is mixed with the stated amountof solvent, and the resulting concentrate is diluted with the statedamount of water which contains the stated emulsifier.

Young apple seedlings in the 4 6 leaf stage are sprayed (treated) withthe active compound spray liquid until dripping wet. The plants remainin a greenhouse for 24 hours at C and at a relative atmospheric humidityof 70 percent. The plants are then inoculated by dusting with conidia ofthe apple powder mildew causative organism (Podosphaera leucotrichasalm.) and placed in a greenhouse at a temperature of 2l-23 C. and at arelative atmospheric humidity of about 70 percent.

Ten days after the inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

0 percent means no infestation; lOO percent means that the infestationis exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 1:

TABLE 1 {Podosphaera test (protectivefl Infestation as a percentage ofthe infestation of the untreated control with a concentration of activecompound (in percent) (E) i N 34 54 s i Cl According to the invention:Active compounds corresponding to formula (I) above in A further testwas carried out in the same manner as Example 1, with the followingresults:

TABLE 2 Podosphaera Test (protective) Infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound (in of Active Compound 0.0062 0.0031 0.00156 R 0 0 10 R m-F O 018 EXAMPLE 3 Erysiphe Test Solvent: 4.7 parts by weight acetoneEmulsifier: 03 parts by weight alkylaryl polyglycol ether Water: 95.0parts by weight The amount of the particular active compound requiredfor the desired concentration in the spray liquid is mixed with thestated amount of the solvent, and the resulting concentrate is dilutedwith the stated amount of water containing the stated emulsifier.

Young cucumber plants (Delikaless variety) with about three foliageleaves are sprayed (treated) with the active compound spray liquid untildripping wet. The cucumber plants Active compound remain in a greenhousefor 24 hours to dry. The plants are Then, for the purpose ofinoculation, dusted with conidia of the fungus Erysiphe polyp/raga. Theplants are subsequently placed in a greenhouse at 23-24 C and at arelative atmospheric humidity of about 75 percent.

After 12 days, the infestation of the cucumber plants is determined as apercentage of the untreated but also inoculated control plants. percentmeans no infestation; 100 per cent means that the infestation is exactlyas great as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 3:

oi thruntrnntcd contrr-l with n cmicvutmtion 0! active compound (inpercent? (ii-- Known:

i Q' i Cl N l l l Cl TABLE 3-Cominued [Eryslphe test] Infestation as anercentace of the infestation of the untreated control with aconcentration of active compound (in percent) of- Active compound 0. 0250. 00078 0. 00019 0. 00009 Known:

(E) H N 20 50 l Q Q .C l

l H l i;

l Br

According to the invention: EXAMPLE 5 Active com unds corres ondin toformula I above in p0 p g 4O Mycelium growth Test which R has thefollowing meaning:

(A) R= p- A further test was carried out in a similar manner as Example3, with the following results:

TABLE 4 Erysiphe Test Infestation as a percentage of the infestation ofthe untreated control with a concentration of active compound (in ofActive Compound 0.025 0,00078 000019000009 R O-F 0 0 3 l3 (9,) R m-F 0 03 Nutrient medium used:

20 parts by weight agar-agar 30 parts by weight malt extract 950 partsby weight distilled water Proportion of solvent to nutrient medium:

2 parts by weight acetone lOO parts by weight agar nutrient medium Theamount of the particular active compound required for the desiredconcentration of such active compound in the nutrient medium is mixedwith the stated amount of solvent. The resulting concentrate isthoroughly mixed, in the stated proportion, with the liquid nutrientmedium (which has been cooled to 42 C) and is then poured into Petridishes of 9 cm diameter. Control dishes to which the active compoundpreparation has not been added are also set up.

When the nutrient medium has cooled and solidified, the dishes areinoculated with the species of fungi stated in the table below andincubated at about 21 C.

Evaluation is carried out after 4-10 days, dependent upon the speed ofgrowth of the fungi. When evaluation is carried out, the radial growthof the mycelium on the treated nutrient media is compared with thegrowth on the control nutrient media. in the evaluation of the fungusgrowth, the following characteristic values are used:

ALAN- o The particular active compounds tested, their concentrations andthe results obtained can be seen from the following Table 5:

'IA BLE 5.MYCELIU.\I GROWTH TEST Fungi Concentra- Phz'alo- Cochlition ofactive Pzricphora Pellu- C'ercoubolus compound ularla clnerculart'a spammiyahe- Active compound in ppm. oryzae escens sasakil musae (mus Known:

According to the invention: Active compounds corresponding to formula(1) above in which R has the following meaning:

The process for producing the particular new compounds of the presentinvention is illustrated, without limitation, by the following furtherexamples:

EXAMPLE 6 156.5 g (0.5 mol) of (p-chlorophenyl)-(dipheny])-methylchloride and 34 g (0.5 mol) imidazole are dissolved in 500 mlacetonitrile, with stirring, and 51 g (0.5 mol) triethylamine are added,whereupon separation of trlethylamine hydrochloride occurs even at roomtemperature. In order to complete the reaction, heating at 50 C iscarried out for 3 hours. After cooling, 1 liter of benzene is added andthe reaction mixture is stirred, then washed salt-free with water. Thebenzene solution is dried over anhydrous sodium sulfate, filtered andconcentrated by evaporation; giving 167 g of crudel-[(pchlorophenyl)-(bisphenyl)-methyl]-imidazole, mp 125 C. Byrecrystallization from 200 ml benzene and 100 ml ligroin, l g 71 percentof the theory) of pure 1-[(p-chlorophenyl)(bis-phenyl)-methyl]-imidazole of m.p. 140 C are obtained.

EXAMPLE '1 34 g (0.5 mol) imidazole are dissolved at room temperature,

with stirring, in a solution of 148.25 g (0.5 mol) of (P over anhydroussodium sulfate, filtered and concentrated by evaporation; giving 148g ofcrude l-[(p-fluorophenyl)- (bisphenyl)-methyl]-imidazole of mp. 146C 91%of the theory). By recrystallization from 300 ml benzene and 50 mlligroin, the nip rises to 148 C.

The (p-fluorophenyl)-(diphenyl)-methyl chloride used as startingmaterial can be prepared as follows: 174.9 g (1 mol)p-fluoro-bromobenzene in 175 m1 ether are slowly added dropwise to 24.3g (l gram-atom) magnesium in 300 ml ether. After all the magnesium isdissolved, a solution of 182 g (1 mol) benzophenone in 500 ml ether isadded dropwise. The magnesium salt of the alcohol separates from theinitially deep-violet solution towards the end of the reaction. Bywashing with 10 percent ammonium chloride solution, the alcohol isobtained which, without isolation, is immediately further processed bydissolving it in 1 liter of benzene, adding 50 g of calcium chloride andintroducing hydrogen chloride gas until saturation. After filtration andremoval of the solvent, the resulting crystal slurry is vigorouslysuction filtered and the crystals obtained are washed with petroleumether. 205 g 69percent of the theory) of (p-fluorophenyl)-(diphenyl)-methyl chloride of m.p. 88 C are obtained.

EXAMPLE 8 27.2 g (0.4 mol) imidazole and 62.8 g (0.2 mol) of(mchlorophenyl )-(diphenyl )-methyl chloride are heated to 80 C for 4hours in 150 ml of dry acetonitrile and 50 ml dimethyl formamide. Thesolvent is then drawn off and the residue is digested with water toremove the imidazole hydrochloride. The residue is taken up in methylenechloride, dried over sodium sulfate, and the viscous oil remainingbehind after the distilling off of the solvent is recrystallized fromcyclohexane. 52 g (75 percent of the theory) of l-[(rn-chlorophenyl)-(bisphenyl)-methyl]-imidazole of mp. 101 C are obtained.

In analogous manner, the following compounds of the general formula (1)above are prepared:

Compound R mp. C.

(7,) o-Cl 140 (6 m-CF l5 6 (3 o-OCH, 130 (5 p-Br l5 2 (12,) p-SCl-l 14210,) -CH l 30 (8 o-F 185 (9 m-F 174 13, p-NO, -170 14,) p-CN 164 It willbe realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicity, enabling such compounds to be used withcorrespondingly favorable compatibility with warm-blooded creatures andplants for more effective control and/or elimination of fungi byapplication of such compounds to such fungi and/or their habitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

l. A method for controlling fungal diseases in plants which comprisesapplying to the fungi or to the plant to be protected a fungicidallyeffective amount ofa compound of the formula:

wherein R is alkyl of one or two carbon atoms substituted by one to fivefluoro moieties.

2 A method according to claim 1, wherein the application is by spraying.

3. A method according to claim 1 wherein the application is byscattering the compound on the fungi or plant to be protected.

4. A method according to claim 1, wherein the application is by dustingthe compound on the fungi or plant to be protected.

5. A method according to claim 1, wherein R is trifluoromethyl.

6. A method according to claim I, wherein R is m-alkyl of one or twocarbon atoms substituted by one to five fluoro moieties.

7. A method according to claim 1 wherein R is mtrifluoromethyl.

r a Page Of 2 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT N0. 3,665,079 DATED May 23, 1972 |'NV.ENTOR(5) IKarl-Heinz Buchel, Erik Regel,Ferdinand Grewe,

he 1 e t sers, It rs certrfred IIrPeIrofiapearfirPtfie Ir fe-r enei rtrpanfi a d that send Letters Patent are hereby corrected as shown below:

In column 1, formula (i) should read 'X In column 6, Table 1 shouldread:

TABLE l.-PODOSPHAERA IEST (PROTECTIVE) Infestation as a percentage ofthe infestation of the untreated control with a concentration of activecompound (in percent) of- Active compound 0.0062 0.0031 0.00156 Knmzgnn(B)--- I 90 I 0 9e: 98 c1gc1 1 Page 2 of 2 UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENTNO. 3, 5,079

DATED M y 1972 V I Karl-HeinzBuchel, Erik Regal, Ferdinand Grewe,

ns Schein flu eln rut Kas ers It rs certlflegfitat error appears In therfive identrfred patent nd that sard Letters Patent 0 are herebycorrected as shown below:

Table 1 (continued) Other compounds tested Signed and Scaled thisTwelfth Day of October 1976 [SEAL] AIICSI.

RUTH C. MASON C. MARSHALL DANN Commissioner oj'lalenrs and TrademarksArresting Officer ggiggi T i rTED ST TES PATENT OFFICE (1E1 TIFICATE orcome Patent No. 3,665,079 Dated May 23,- 1972 Inventor(s) Karl-HeinzBuchel, Erik Regel, Federinand Grewe,

Hans Scheinpflug and Helmut Kaspers It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

F Column 14, following line, add claims 8 and 9 as vfollows T I 8. Amethod according to claim 1 wherein R is mono-, dior tri-fluoromethyl.

9. A method according to claim 1 wherein R ismono-, di-, tri-, tetraorpenta-fluoroethyl.

Signedand sealed this 23rd day of January 1973..

(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBE RT GOTTSCHALK Attesting Officer Commissionerof Patents

2. A method according to claim 1, wherein the application is byspraying.
 3. A method according to claim 1 wherein the application is byscattering the compound on the fungi or plant to be protected.
 4. Amethod according to claim 1, wherein the application is by dusting thecompound on the fungi or plant to be protected.
 5. A method according toclaim 1, wherein R is trifluoromethyl.
 6. A method according to claim 1,wherein R is m-alkyl of one or two carbon atoms substituted by one tofive fluoro moieties.
 7. A method according to claim 1 wherein R ism-trifluoromethyl.